Comparison of Implicit and Explicit Solvent Approaches in Ab Initio Evaluation of Thermochemistry in Solution: Application in Studying Boron Isotope Fractionation in Water.

Evaluation of thermochemistry in solution plays a key role in numerous fields. For this task, the solvent effects are commonly included in theoretical computations based on either implicit or explicit solvent approaches. In the present study, we evaluate and compare the performance of some of the most widely applied methods based on these two approaches. For studying the solvent effect on thermochemistry with an explicit solvent, we demonstrate that partial normal mode analysis with frozen geometry of solvent molecules for multiple solute-solvent configurations can yield quite accurate and reliable results for a drastically reduced computational cost. As a case study, we consider the evaluation of the equilibrium constant for the boron isotope exchange between boric acid and borate ( k 3-4 ) in pure and saline water which is of high geochemical importance. Employing three different rigorous and high-precision theoretical approaches, we provide a reliable estimation of k 3-4 which is a value within 1.028 to 1.030 for both pure and saline water which is in excellent agreement with experimental data.